Coating composition and laminate

Abstract

To provide an emulsion type coating composition that does not deteriorate performance of an emulsion of a vinyl chloride resin, an acrylic resin, and an urethane resin, imparts performance inherent to a silicone resin, and solves the problem related to a cost.SOLUTION: A coating composition contains the following component (I) and component (II). (I): An emulsion of a vinyl chloride resin, an acrylic resin, and / or an urethane resin. (II): A vinyl chloride-silicone graft copolymer resin emulsion which is a polymer formed by (A) an organopolysiloxane and (B) vinyl chloride at a mass ratio of (A):(B)=5:95 to 95:5.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a coating composition, and more particularly to an emulsion-type coating composition that can maintain transparency and impart slidability by coating a substrate surface. The present invention also relates to a laminate having a film formed by this coating composition.

Background Art

[0002] In recent years, in the field of coating agents, the dispersion medium has been shifting from organic solvent-based to water-based in terms of environmental issues. Emulsions such as vinyl chloride resins, acrylic resins, and urethane resins have excellent film-forming ability and have been widely used as coating agents.

[0003] In addition, silicone-based resins are known as resins that can impart slidability to a substrate. However, when a silicone-based resin is used as a coating agent, there are problems such as whitening of the coating film.

[0004] As emulsions of silicone-modified resins, emulsions of copolymers such as acrylic silicone emulsions and urethane silicone emulsions are known. These can impart advantages such as weather resistance, heat resistance, cold resistance, water repellency, gas permeability, and slidability of silicone to the performance of emulsions of acrylic resins or urethane resins. However, there are also demerits such as not only an increase in cost due to the copolymer but also a decrease in the advantages of the resin before modification.

[0005] Therefore, a method of mixing an emulsion of a vinyl chloride resin, an acrylic resin, or a urethane resin having film-forming ability with a silicone-based resin and using it as a coating agent has been attempted. However, in some cases, satisfactory performance cannot be exhibited due to the inability to exhibit the slidability of the silicone-based resin or the deterioration of the performance of the original urethane resin, acrylic resin, and vinyl chloride resin by mixing.

[0006] For example, in JP-A-2013-067787 (Patent Document 1) and JP-A-2020-090596 (Patent Document 2), it is disclosed that a coating agent obtained by mixing an emulsion of a vinyl chloride-based resin, an acrylic-based resin, or a urethane-based resin with a silicone-based resin can impart water repellency and transparency to a substrate. However, there was room for improvement in the silicone-based resin in terms of transparency, water repellency, slidability, and cost.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0008] Therefore, an object of the present invention is to provide an emulsion-type coating composition that imparts the performance of a silicone-based resin without degrading the performance of an emulsion of a vinyl chloride-based resin, an acrylic-based resin, and a urethane-based resin, and also solves the cost problem, and a laminate having a film formed from the composition.

Means for Solving the Problems

[0009] As a result of intensive studies to achieve the above object, the present inventors have found that a coating composition obtained by blending (I) at least one resin emulsion selected from a vinyl chloride-based resin emulsion, an acrylic-based resin emulsion, and a urethane-based resin emulsion and (II) a vinyl chloride-silicone graft copolymer resin in a predetermined ratio can solve the above problems, and have completed the present invention.

[0010] That is, the present invention provides the following coating composition, its film, and a laminate.

[0011] [1] A coating composition containing the following component (I) and component (II). (I) At least one emulsion selected from a vinyl chloride resin emulsion, an acrylic resin emulsion, and a urethane resin emulsion: 60 to 99% by mass of solid content (II) A graft copolymer of (A) an organopolysiloxane represented by the following formula (1) and (B) vinyl chloride, wherein the mass ratio of (A) the organopolysiloxane to (B) vinyl chloride is (A):(B) = 5:95 to 95:5, a vinyl chloride-silicone graft copolymer resin emulsion: 1 to 40% by mass of solid content [Chemical formula] (In formula (1), R 1 is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 2 is a radical-reactive functional group. X is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group. Y is the same or different group represented by X or -[O-Si(X)2] d -X. Z is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. a is a number from 0 to 10,000, b is a number from 100 to 10,000, c is a number from 0.0001 to 100, and d is a number from 1 to 1,000.) [2] The cured product of the coating composition according to [1]. [3] The cured product according to [2], wherein the cured product is a coating film. [4] A laminate having the cured product according to [2]. [5] A laminate having the cured product according to [3]. [Advantages of the Invention]

[0012] The coating composition of the present invention has excellent transparency, water repellency, and slidability, and can maintain high abrasion resistance without impairing the appearance of a laminate having a film formed from the coating composition. Further, since the dispersion medium of the coating composition of the present invention is aqueous, it has great advantages in terms of the working surface and the environment. [Embodiments for Carrying Out the Invention]

[0013] (I) The emulsion selected from a vinyl chloride resin emulsion, an acrylic resin emulsion, and a urethane resin emulsion may be used alone or in combination of two or more. The emulsion of component (I) may be synthesized by a known method, for example, an emulsion polymerization method using an anionic surfactant or a nonionic surfactant, etc., or a commercially available product may be used. The above emulsion has a film-forming ability. The film-forming ability is a performance in which the particle property on the surface of the dried coating film disappears at a certain temperature or higher and no fine cracks occur during drying. The drying temperature range for film formation is not particularly limited, but is preferably 30 to 150°C, more preferably 100 to 150°C. Also, the drying time is not particularly limited, but is preferably about 1 second to 10 hours. For the emulsion selected from the vinyl chloride resin emulsion, the acrylic resin emulsion, and the urethane resin emulsion of component (I) to have a film-forming ability, the average particle diameter of the emulsion is preferably 10 to 500 nm. The average particle diameter is measured by a dynamic light scattering type particle diameter distribution measuring device. The viscosity (25°C) of the emulsion of component (I) is preferably 10 to 500 mPa·s. The viscosity can be measured with a rotational viscometer.

[0014] Since the emulsion selected from the vinyl chloride resin emulsion, the acrylic resin emulsion, and the urethane resin emulsion of component (I) has a film-forming ability, the average particle diameter of the emulsion is preferably 10 to 500 nm. The average particle diameter is measured by a dynamic light scattering type particle diameter distribution measuring device. The viscosity (25°C) of the emulsion of component (I) is preferably 10 to 500 mPa·s. The viscosity can be measured with a rotational viscometer. In addition, the glass transition temperature (hereinafter sometimes referred to as Tg) of the emulsion of component (I) is 120°C or lower, preferably 60°C or lower, and more preferably 30°C or lower. The lower limit of the glass transition temperature is preferably -50°C. The glass transition temperature can be measured based on JIS K7121.

[0015] Vinyl chloride resin emulsion The vinyl chloride resin emulsion of component (I) may be an emulsion of not only a homopolymer of a vinyl chloride monomer but also a copolymer (copolymer resin) of a vinyl chloride monomer and a vinyl acetate monomer or a vinyl chloride monomer and an acrylic monomer used in the following acrylic resin emulsion.

[0016] Acrylic resin emulsion In addition, the acrylic resin emulsion of component (I) is an emulsion of a copolymer (copolymer resin) obtained by mixing one or more of the following monomers. Examples of the acrylic resin monomer include (meth)acrylic acid esters with alcohols having an alkyl group with 1 to 18 carbon atoms, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, glycidyl (meth)acrylate, allyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, etc. Note that (meth)acrylate is a general term for acrylate and methacrylate. In addition to the above, the following monomers may be used in combination. Examples of such monomers include acrylonitrile, vinyl acetate, vinyl propionate, styrene, acrylic acid, methacrylic acid, (meth)acrylamide, N-methylol (meth)acrylamide, N-methoxymethyl (meth)acrylamide, etc.

[0017] Urethane resin emulsion The urethane resin emulsion may be not only a homopolymer composed of molecules having a urethane bond or an isocyanurate bond, but also an emulsion of a copolymer (copolymer resin) with an acrylic monomer, a silane monomer, an epoxy monomer, a polyester polymer, or a urea polymer.

[0018] Specific examples of the emulsion include vinyl chloride-based resin emulsions using vinyl chloride, vinyl chloride / vinyl acetate, vinyl chloride / (meth)acrylic acid or its esters, etc., acrylic resin emulsions using (meth)acrylic monomers such as (meth)acrylic acid and (meth)acrylic acid esters, and urethane resin emulsions.

[0019] Examples of commercially available vinyl chloride-based resin emulsions include Vinibran manufactured by Nissin Chemical Industry Co., Ltd. Examples of commercially available acrylic resin emulsions include Vinibran manufactured by Nissin Chemical Industry Co., Ltd., Yodzol manufactured by Henkel Japan Co., Ltd., and Aron manufactured by Toagosei Co., Ltd. Examples of commercially available urethane resin emulsions include Adeka BonタイターHUX series manufactured by ADEKA Corporation, WLS series manufactured by DIC Corporation, and Eucort manufactured by Sanyo Chemical Industries, Ltd.

[0020] The blending amount of the emulsion selected from the vinyl chloride-based resin emulsion, acrylic resin emulsion, and urethane resin emulsion of component (I) is 60 to 99% by mass, preferably 65 to 95% by mass, in terms of solid content in the coating composition. If this emulsion is less than 60% by mass, the film properties such as abrasion resistance may deteriorate, and if it exceeds 99% by mass, the surface may not be smooth, resulting in poor touch.

[0021] (II) The vinyl chloride-silicone graft copolymer resin emulsion is obtained by graft copolymerizing (A) an organopolysiloxane represented by the following general formula (1) and (B) vinyl chloride, and is a vinyl chloride-silicone graft copolymer resin emulsion in which the mass ratio of the above (A) organopolysiloxane to the above (B) vinyl chloride is (A):(B) = 5:95 to 95:5.

[0022] In the present invention, the (A) organopolysiloxane is represented by the following formula (1).

Chemical formula

[0023] Here, R 1 is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, etc., cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, etc., alkenyl groups such as vinyl group, allyl group, etc., aryl groups such as phenyl group, tolyl group, naphthyl group, etc., alkenylaryl groups such as vinylphenyl group, etc., aralkyl groups such as benzyl group, phenylethyl group, phenylpropyl group, etc., alkenylaralkyl groups such as vinylbenzyl group, vinylphenylpropyl group, etc., and those in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, bromine, chlorine, etc., acryloxy group, methacryloxy group, carboxyl group, alkoxy group, alkenyloxy group, amino group, alkyl or alkoxy or (meth)acryloxy-substituted amino group, etc. are mentioned. R 1 is preferably a methyl group.

[0024] R2 is a radical-reactive functional group, and a mercapto group or an alkyl group having 1 to 8 carbon atoms substituted with an ethylenic double bond-containing group is preferable. Specifically, it is an alkyl group having 1 to 8 carbon atoms substituted with a vinyl group, a styryl group, a mercapto group, an acryloxy group or a methacryloxy group. Examples include a vinyl group, a styryl group, an octenyl group, a methacryloxyoctyl group, a mercaptopropyl group, an acryloxypropyl group, a methacryloxypropyl group, a methacryloxyoctylvinyl group and the like.

[0025] X is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or a hydroxyl group. As the unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, those exemplified by R 1 can be exemplified by the same ones as those exemplified above. As the alkoxy group having 1 to 20 carbon atoms, specifically, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group, a tetradecyloxy group and the like can be mentioned. Among these, a hydroxyl group, a methyl group, a butyl group and a phenyl group are preferable. Y is the same or different group represented by X or -[O-Si(X)2] d -X. As the X, the same ones as those exemplified above can be exemplified.

[0026] Z is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group, preferably a hydroxyl group or a methyl group.

[0027] a is a number from 0 to 10,000, preferably a number from 0 to 1,000, more preferably a number from 0 to 200. When constituting the a unit, the lowest limit may be 0.5. When a is larger than 10,000, the strength of the coating film obtained when the composition containing the component (A) is used as a coating film may be insufficient. b is a number from 100 to 10,000, preferably a number from 1,000 to 5,000. If b is less than 100, the flexibility of the film may be poor, and if it is greater than 10,000, its tear strength may decrease. c is a number from 0.0001 to 100. If it exceeds 100, the sliding effect may not be exerted. Here, c / (a + b + c)×100 is preferably from 0.0001 to 10, more preferably from 0.001 to 10. d is a number from 1 to 1,000, preferably a number from 1 to 200.

[0028] The organopolysiloxane represented by the above formula (1) is preferably used in the form of an emulsion. A commercially available product may be used, or it may be synthesized. When synthesizing, it can be synthesized by a known emulsion polymerization method. For example, cyclic organosiloxane or α,ω-dihydroxysiloxane oligomer, α,ω-dialkoxysiloxane oligomer, alkoxysilane, etc., and the silane coupling agent represented by the following formula (2) are emulsified and dispersed in water using an anionic surfactant, and then a polymerization catalyst such as an acid is added as necessary to carry out a polymerization reaction, and it can be easily synthesized. The cyclic organosiloxane may have a fluorine atom, a (meth)acryloxy group, a carboxyl group, a hydroxyl group, or an amino group. [Chemical formula] (In formula (2), R 3 is a radical-reactive functional group. In particular, it represents an acryloxy group, a methacryloxy group, a vinyl group, or a mercapto group-substituted alkyl group having 1 to 8 carbon atoms, or a styryl group or a vinyl group. R 4 is an alkyl group having 1 to 4 carbon atoms or a hydroxyl group, R 5 is an alkyl group having 1 to 4 carbon atoms, e is 2 or 3, f is 0 or 1, and e + f is 2 or 3.)

[0029] Examples of the cyclic organosiloxane include hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), 1,1 - diethylhexamethylcyclotetrasiloxane, phenylheptamethylcyclotetrasiloxane, 1,1 - diphenylhexamethylcyclotetrasiloxane, 1,3,5,7 - tetravinyltetramethylcyclotetrasiloxane, 1,3,5,7 - tetramethylcyclotetrasiloxane, 1,3,5,7 - tetracyclohexyltetramethylcyclotetrasiloxane, tris(3,3,3 - trifluoropropyl)trimethylcyclotrisiloxane, 1,3,5,7 - tetra(3 - methacryloxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7 - tetra(3 - acryloxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7 - tetra(3 - carboxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7 - tetra(3 - vinyloxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7 - tetra(p - vinylphenyl)tetramethylcyclotetrasiloxane, 1,3,5,7 - tetra[3-(p - vinylphenyl)propyl]tetramethylcyclotetrasiloxane, 1,3,5,7 - tetra(N - acryloyl - N - methyl - 3 - aminopropyl)tetramethylcyclotetrasiloxane, 1,3,5,7 - tetra(N,N - bis(lauroyl)-3 - aminopropyl)tetramethylcyclotetrasiloxane, and the like. Preferably, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane are used.

[0030] As silane coupling agents, specifically, vinyl silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane; acrylic silanes such as γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, γ-(meth)acryloxypropyltripropoxysilane, γ-(meth)acryloxypropyltriisopropoxysilane, γ-(meth)acryloxypropyltributoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, γ-(meth)acryloxypropylmethyldiethoxysilane, γ-(meth)acryloxypropylmethyldipropoxysilane, γ-(meth)acryloxypropylmethyldiisopropoxysilane, γ-(meth)acryloxypropylmethyldibutoxysilane; mercapto silanes such as γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane; styryl silanes such as styryltrimethoxysilane and the like can be mentioned. Further, oligomers obtained by condensation polymerization of these may be more preferable as the generation of alcohol is suppressed. Here, (meth)acryloxy represents acryloxy or methacryloxy. These silane coupling agents are preferably used in an amount of 0.01 to 20 parts by mass, more preferably 0.01 to 5 parts by mass, based on 100 parts by mass of cyclic organosiloxane or α,ω-dihydroxysiloxane oligomer, α,ω-dialkoxysiloxane oligomer, alkoxysilane, etc.

[0031] By copolymerizing cyclic organosiloxane or α,ω-dihydroxysiloxane oligomer, α,ω-dialkoxysiloxane oligomer, alkoxysilane, etc. with a silane coupling agent, an organopolysiloxane having a unit ([Si(R 2 )(Z)O] represented by the unit) in the repeating number c in the above formula (1) is obtained, and (B) vinyl chloride can be graft polymerized.

[0032] As the polymerization catalyst, a known polymerization catalyst may be used. Among them, strong acids are preferred, and hydrochloric acid, sulfuric acid, dodecylbenzenesulfonic acid, citric acid, lactic acid, and ascorbic acid are exemplified. Dodecylbenzenesulfonic acid having surfactant properties is preferred. The amount of the acid catalyst used is preferably 0.01 to 10 parts by mass, more preferably 0.2 to 2 parts by mass, based on 100 parts by mass of the cyclic organosiloxane or α,ω-dihydroxysiloxane oligomer, α,ω-dialkoxysiloxane oligomer, alkoxysilane, etc.

[0033] As the anionic surfactant, sodium lauryl sulfate, sodium laureth sulfate, N-acyl amino acid salt, N-acyl taurine salt, fatty soap, alkyl phosphate, sodium lauroyl methyl taurine, sodium myristoyl methyl taurine, etc. are preferred. More preferably, N-acyl amino acid salt, N-acyl taurine salt, fatty soap, alkyl phosphate, sodium lauroyl methyl taurine, sodium myristoyl methyl taurine, and particularly preferably, sodium lauroyl methyl taurine, sodium myristoyl methyl taurine, and sodium lauryl sulfate.

[0034] The amount of the anionic surfactant used is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the cyclic organosiloxane or α,ω-dihydroxysiloxane oligomer, α,ω-dialkoxysiloxane oligomer, alkoxysilane, etc.

[0035] The polymerization temperature is preferably 50 to 75 °C, the polymerization time is preferably 10 hours or more, more preferably 15 hours or more. Further, it is particularly preferred to age at 5 to 30 °C for 10 hours or more after polymerization.

[0036] After completion of the polymerization reaction, it may be neutralized to pH 2.5 to 14, preferably 4 to 11, using a neutralizing agent (such as a 10% aqueous sodium carbonate solution).

[0037] (A) The weight average molecular weight (Mw) of the organopolysiloxane as measured by viscosity is preferably from 10,000 to 1,000,000, more preferably from 100,000 to 500,000, in terms of the sliding effect.

[0038] Here, the weight average molecular weight (Mw) of the organopolysiloxane as measured by viscosity is calculated from the specific viscosity ηsp (25 °C) of a toluene solution of the organopolysiloxane at a concentration of 1 g / 100 ml. ηsp = (η / η0) - 1 (η0: viscosity of toluene, η: viscosity of the solution) ηsp = [η] + 0.3[η] 2 [η] = 0.215 × 10 -4 M 0.65 Specifically, 20 g of the emulsion is mixed with 20 g of IPA (isopropyl alcohol), and after destroying the emulsion, the IPA is discarded, and the remaining rubbery organopolysiloxane is dried at 60 °C overnight. This is used as a toluene solution of the organopolysiloxane at a concentration of 1 g / 100 ml, and the measurement is carried out at 25 °C using an Ubbelohde viscometer. The molecular weight can be determined by substituting the viscosity into the above formula (References: Nakamuta, Nippon Kasei Kagaku Kaishi, 77, 858

[1956] , Doklady Akad. Nauk. U.S.S.R. 89, 65

[1953] ).

[0039] The vinyl chloride-silicone graft copolymer (copolymer resin) can be obtained by graft polymerizing (A) an organopolysiloxane and (B) vinyl chloride.

[0040] The method for producing the vinyl chloride-silicone graft copolymer (copolymer resin) has a step of graft polymerizing the organopolysiloxane of formula (1) ((A) component) and vinyl chloride ((B) component) in a mass ratio (mass ratio of the organopolysiloxane of formula (1) to the vinyl chloride unit) of 5:95 to 95:5, preferably 20:80 to 85:15. If the proportion of the organopolysiloxane component of formula (1) is less than 5 as described above, the sliding effect may not be exhibited.

[0041] Examples of the radical initiator used in the production of vinyl chloride-silicone graft copolymer (copolymer resin) include persulfates such as potassium persulfate and ammonium persulfate, hydrogen persulfate, t-butyl hydroperoxide, and hydrogen peroxide. If necessary, a redox compound in which a reducing agent such as sodium bisulfite, Rongalit, L-ascorbic acid, tartaric acid, saccharides, and amines is used in combination can also be used. In addition, the amount of the radical initiator used is preferably 0.1 to 5% by mass, more preferably 0.5 to 3% by mass, based on (B) vinyl chloride.

[0042] The polymerization temperature of component (B) with respect to component (A) is preferably 25 to 85°C, more preferably 55 to 85°C. The polymerization time is preferably 2 to 20 hours, more preferably 3 to 10 hours.

[0043] Furthermore, a chain transfer agent can be added to adjust the molecular weight and polymerization rate of the polymer. Examples thereof include halogenated hydrocarbons such as chloroform and carbon tetrachloride; and mercaptans such as n-dodecyl mercaptan, tert-dodecyl mercaptan, and n-octyl mercaptan. The amount of the chain transfer agent used is preferably 0.1 to 1 part by mass, more preferably 0.3 to 0.8 part by mass, per 100 parts by mass of the monomer.

[0044] The vinyl chloride-silicone graft copolymer (copolymer resin) thus obtained is a polymer in which (B) vinyl chloride is randomly bonded to (A) organopolysiloxane, and is a polymer in which various structures are mixed, and it is impossible to directly specify the product by its structure or properties.

[0045] The method for producing an emulsion of a vinyl chloride-silicone graft copolymer (copolymer resin) preferably includes a step of emulsion polymerization of an organopolysiloxane ((A) component) of formula (1) and vinyl chloride ((B) component) at a mass ratio (mass ratio of the organopolysiloxane of formula (1) to vinyl chloride units) of 5:95 to 95:5, preferably 20:80 to 85:15. It is sufficiently graft polymerizable with the surfactant contained in the organopolysiloxane emulsion. However, as an anionic surfactant for improving stability, sodium lauryl sulfate, sodium laureth sulfate, N-acyl amino acid salt, N-acyl taurine salt, fatty soap, alkyl phosphate, etc. can be added. Also, nonionic emulsifiers such as polyoxyethylene lauryl ether and polyoxyethylene tridecyl ether can be added. The amount used when adding a surfactant is preferably 0.1 to 5% by mass of (B) vinyl chloride.

[0046] Also, the vinyl chloride-silicone graft copolymer (copolymer resin) preferably has a solid content of the emulsion of 25 to 40% by mass. Also, the viscosity (25 °C) of this emulsion is preferably 1 to 500 mPa·s, more preferably 1 to 200 mPa·s. The viscosity can be measured with a rotational viscometer. The average particle diameter of the emulsion is preferably 0.1 μm (100 nm) to 0.5 μm (500 nm). The average particle diameter is a value measured by a dynamic light scattering particle size distribution measuring device.

[0047] The blending amount of the vinyl chloride-silicone graft copolymer resin emulsion of component (II) is 1 to 40% by mass, preferably 5 to 30% by mass, in terms of solid content in the coating composition. If the vinyl chloride-silicone graft copolymer resin emulsion is less than 1% by mass, there may be no improvement in abrasion resistance at all. If it exceeds 40% by mass, whitening may occur and the abrasion resistance may also decrease.

[0048] The coating composition of the present invention is obtained by mixing, under an aqueous system, an emulsion selected from the vinyl chloride resin emulsion, acrylic resin emulsion, and urethane resin emulsion of component (I) and the vinyl chloride-silicone graft copolymer resin emulsion of component (II) by a known mixing and preparation method such as a propeller stirrer or a homogenizer.

[0049] In addition, antioxidants, colorants, ultraviolet absorbers, light stabilizers, antistatic agents, plasticizers, flame retardants, thickeners, surfactants, organic solvents (such as film-forming aids), other resins, etc. may be added to the coating composition of the present invention as long as they do not affect the performance.

[0050] A laminate can be obtained by applying or dipping the coating composition of the present invention on one or both sides of a substrate.

[0051] Regarding the coating composition of the present invention, from the viewpoint of ensuring a desired high transparency, it is preferable that the haze increase rate when applied to the substrate is 1500% or less with respect to the haze value of the substrate before coating. Depending on the type of the substrate, it is more preferably 1000% or less. "Haze" as used in the present invention is the HAZE (cloudiness value) calculated by the following formula from the total light transmittance and the diffuse transmittance in accordance with the standard of JIS K7136 (2000). HAZE (cloudiness value) = (diffuse transmittance T d / total light transmittance T t ) × 100 (%) The haze value after application to the substrate can be measured, for example, by a haze meter manufactured by Nippon Denshoku Industries Co., Ltd. Also, the haze value of the substrate before application of the coating composition can be measured according to the same standard as above. In addition, "haze increase rate" as used in the present invention can be calculated from the following formula, where the haze value of the substrate is H X , and the haze value after application of the coating composition is H Y . [Haze value increase rate (%)] = [(H Y - H X ) / H X × 100

[0052] When the coating composition of the present invention is applied or immersed on one or both sides of a substrate such as plastic (PET, PI, etc.), glass (general-purpose glass, SiO2, etc.), metal (Si, Cu, Fe, Ni, Co, Au, Ag, Ti, Al, Zn, Sn, Zr, their alloys, etc.), wood, fiber (cloth, thread, etc.), paper, ceramic (fired products such as oxides, carbides, nitrides, etc.), and then dried (room temperature to 150 °C), while maintaining the advantages of acrylic resins, vinyl chloride resins, or urethane resins, the advantages of silicone resins such as water repellency, weather resistance, heat resistance, cold resistance, gas permeability, and slidability can be imparted over a long period of time. In this specification, room temperature refers to 1 °C to 40 °C.

[0053] Here, as the plastic substrate, poly(meth)acrylate esters such as polymethyl methacrylate, polycarbonate, polystyrene, polyethylene terephthalate, polyvinyl chloride, polyester, cellulose, diethylene glycol bisallyl carbonate polymer, acrylonitrile-butadiene-styrene polymer, polyurethane, and epoxy resin are used. Examples of plastic processed products include automotive interior materials, organic glass, electrical materials, building materials, exterior materials for buildings, optical films, light diffusion films used in liquid crystal displays, mobile phones, and home appliances. As a method of drying, a method of leaving it to stand at room temperature for 1 to 10 days can be mentioned, but from the viewpoint of rapidly promoting curing, a method of heating at a temperature of 20 to 150 °C for 1 second to 10 hours is preferable. Further, when the plastic substrate is made of a material that is likely to be deformed or discolored by heating, it is preferable to dry it at a relatively low temperature of 20 to 100 °C.

[0054] As the glass substrate, soda-lime glass, quartz glass, lead glass, borosilicate glass, alkali-free glass, etc. are used. As glass processed products, there are architectural plate glass, glass for vehicles such as automobiles, glass for lenses, glass for mirrors, glass for display panels, glass for solar cell modules, etc. As a method of drying, it is preferable to leave it at room temperature for about 1 to 10 days or to heat it at a temperature of 20 to 150 °C, particularly 60 to 150 °C, for 1 second to 10 hours.

[0055] As the wood substrate, woods such as those of the Salicaceae, Betulaceae, Lauraceae, Fagaceae, Euphorbiaceae, Taxodiaceae, Ulmaceae, Bignoniaceae, Rosaceae, Cupressaceae, Juglandaceae, Myrtaceae, Fagaceae, Pinaceae, Leguminosae, Oleaceae, etc. are used. As wood processed products, they may be selected from processing and molded products using the wood itself as a raw material, plywood, laminated wood, and their processing and molded products, and combinations thereof. For example, there are building materials for the exterior and interior of buildings, including building materials for construction, furniture such as desks, wooden toys, musical instruments, etc. A method of hot air drying at 20 to 150 °C, particularly 50 to 150 °C for 0.5 to 5 hours is preferable. Also, if the drying temperature is 120 °C or lower, discoloration of the coating film can be avoided.

[0056] Examples of the fiber substrate include natural fibers such as cotton, hemp, linen, wool, silk, cashmere, asbestos, etc. and chemical fibers such as polyamide, polyester, viscose, cellulose, glass, carbon, etc. As fiber processed products, there are all kinds of woven fabrics, knitted fabrics, non-woven fabrics, or films, papers, etc. As a method of drying, it is preferable to leave it at room temperature for 10 minutes to several tens of hours or to dry it at a temperature of 20 to 150 °C for 0.5 minutes to 5 hours.

[0057] The viscosity (23 °C) of the finally obtained composition is preferably 10 mPa·s or more and 3,000 mPa·s or less, and more preferably 20 mPa·s or more and 2,500 mPa·s or less. Note that this viscosity is a value measured by a B-type viscometer (23 ± 0.5 °C). In addition, the composition can be effectively utilized in both alkaline and acidic environments with a pH ranging from 2 to 12 by incorporating a base or an acidic compound.

[0058] Moreover, the method of coating the substrate is not particularly limited, and examples include methods such as direct immersion, spray coating, bar coater, and roll coater. Considering transparency, the film thickness after drying is preferably about 0.5 to 50 μm, more preferably 1 to 20 μm. In the case of film formation by immersion, immerse for 10 seconds to 30 minutes and dry at room temperature to 150 °C for about 1 second to 10 days while appropriately adjusting to obtain a desired thickness, preferably 0.01 to 5 kg / m 2 and process accordingly.

[0059] In the case of film formation by coating, the coating amount of the coating composition of the present invention on the substrate is not particularly limited, but usually, from the viewpoints of antifouling property and workability, in terms of solid content conversion, it is preferably 1 to 300 g / m 2 , more preferably 5 to 100 g / m 2 in the range or a thickness of 1 to 500 μm, preferably 5 to 100 μm, and it is advisable to form a film by natural drying or heat drying at 100 to 200 °C.

[0060] The water contact angle of the obtained film is preferably 50° or more 30 seconds after contact when a droplet of 1.8 μL of ion-exchanged water is brought into contact using an automatic contact angle meter CA-V (manufactured by Kyowa Interface Science Co., Ltd.) in an atmosphere of 23 °C and 45% humidity.

Examples

[0061] Hereinafter, production examples, examples, and comparative examples are shown to specifically illustrate the present invention, but the present invention is not limited to the following production examples and examples. In addition, the molecular weights described below are weight average molecular weights (Mw) determined by viscosity measurement obtained from the specific viscosity of a toluene solution of organopolysiloxane at a concentration of 1 g / 100 ml. In the following examples, "parts" and "%" represent parts by mass and mass %, respectively.

[0062] [Production Example 1] 1200 g of octamethylcyclotetrasiloxane, 4.8 g of γ-methacryloxypropylmethyldimethoxysilane, a solution prepared by dissolving 12 g of sodium lauryl sulfate in 108 g of pure water, and a solution prepared by dissolving 12 g of dodecylbenzenesulfonic acid in 108 g of pure water were charged into a 4 L polyethylene beaker and emulsified uniformly with a homomixer. Then, 728 g of water was gradually added and diluted, and the mixture was passed through a high-pressure homogenizer at a pressure of 300 kgf / cm 2 twice to obtain a uniform white emulsion. This emulsion was transferred to a 2 L glass flask equipped with a stirrer, a thermometer, and a reflux condenser, and a polymerization reaction was carried out at 55 °C for 24 hours. After aging at 15 °C for 24 hours, it was neutralized to pH 7 with a 10% aqueous sodium carbonate solution. The non-volatile content (solid content) of this emulsion after drying at 105 °C for 3 hours was 44%, and the organopolysiloxane in the emulsion was in a non-flowing soft gel state. This emulsion (silicone composition) had a structure represented by the following formula (A) with a molecular weight of about 250,000 as determined from the viscosity of the toluene solution. In formula (A), R 2 is a γ-methacryloxypropyl group. The structure of the organopolysiloxane obtained by the above polymerization reaction was 1 confirmed by 1H-NMR (frequency 600 MHz, room temperature, number of integrations 128 times) and 29 29Si-NMR (frequency 60 MHz, room temperature, number of integrations 5000 times) (apparatus name: JNM-ECA600, measurement solvent: CDCl3). [Chemical formula] 1207 g of the above emulsion was transferred to a polymerization vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen gas inlet. 59 g of vinyl chloride and ammonium persulfate were added, and a reaction was carried out at 60 °C for 8 hours to graft-copolymerize vinyl chloride onto the above silicone composition, obtaining an emulsion of a vinyl chloride-silicone graft copolymer with a non-volatile content of 30%. The obtained vinyl chloride-silicone graft copolymer was a vinyl chloride-silicone graft copolymer in which vinyl chloride was grafted onto R 2 of formula (A).

[0063] [Production Example 2] An emulsion of a vinyl chloride-silicone graft copolymer with a nonvolatile content of 30% was obtained in the same manner except that the amount of vinyl chloride in Production Example 1 was changed to 132 g.

[0064] [Production Example 3] An emulsion of a silicone-vinyl chloride graft copolymer with a nonvolatile content of 30% was obtained in the same manner except that the amount of vinyl chloride in Production Example 1 was changed to 226 g.

[0065] [Production Example 4] 1200 g of octamethylcyclotetrasiloxane, 0.96 g of γ-methacryloxypropylmethyldimethoxysilane, a solution of 12 g of sodium lauryl sulfate dissolved in 108 g of pure water, and a solution of 12 g of dodecylbenzenesulfonic acid dissolved in 108 g of pure water were charged into a 4 L polyethylene beaker, emulsified uniformly with a homomixer, then 728 g of water was gradually added for dilution, and the mixture was passed through a high-pressure homogenizer at 300 kgf / cm 2 twice to obtain a uniform white emulsion. This emulsion was transferred to a 2 L glass flask equipped with a stirrer, thermometer and reflux condenser, and a polymerization reaction was carried out at 55 °C for 24 hours, then aged at 15 °C for 24 hours and then neutralized to pH 7 with a 10% aqueous sodium carbonate solution. The nonvolatile content (solid content) of this emulsion after drying at 105 °C for 3 hours was 45%, and the organopolysiloxane in the emulsion was a non-flowing soft gel. This emulsion (silicone composition) had a structure represented by the following formula (B) with a molecular weight of about 250,000 from the viscosity of the toluene solution. In formula (B), R 2 is a γ-methacryloxypropyl group. [Chemical formula] 1198 g of the above emulsion was transferred to a polymerization vessel equipped with a stirrer, condenser, thermometer and nitrogen gas inlet, 231 g of vinyl chloride and ammonium persulfate were added, and a reaction was carried out at 60 °C for 8 hours to graft-copolymerize vinyl chloride onto the above silicone composition, obtaining an emulsion of a vinyl chloride-silicone graft copolymer with a nonvolatile content of 30%. The obtained vinyl chloride-silicone graft copolymer has R in formula (B)2 The vinyl chloride-silicone graft copolymer in which vinyl chloride is graphed is as follows.

[0066] [Production Example 5] An emulsion of a vinyl chloride-silicone graft copolymer with a nonvolatile content of 30% was obtained in the same manner except that the amount of vinyl chloride in Production Example 1 was changed to 528 g.

[0067] [Production Example 6] An emulsion of a vinyl chloride-silicone graft copolymer with a nonvolatile content of 30% was obtained in the same manner except that the amount of vinyl chloride in Production Example 1 was changed to 1232 g.

[0068] [Comparative Production Example 1] 1200 g of octamethylcyclotetrasiloxane, 4.8 g of γ-methacryloxypropylmethyldimethoxysilane, a solution of 12 g of sodium lauryl sulfate in 108 g of pure water, and a solution of 12 g of dodecylbenzenesulfonic acid in 108 g of pure water were charged into a 4 L polyethylene beaker, emulsified uniformly with a homomixer, then 728 g of water was gradually added and diluted, and the mixture was passed through a high-pressure homogenizer at 300 kgf / cm 2 twice to obtain a uniform white emulsion. This emulsion was transferred to a 2 L glass flask equipped with a stirrer, thermometer and reflux condenser, and after carrying out a polymerization reaction at 55 °C for 24 hours, aging was carried out at 15 °C for 24 hours and then neutralized to pH 7 with a 10% aqueous sodium carbonate solution. The nonvolatile content (solid content) of this emulsion after drying at 105 °C for 3 hours was 44%, and the organopolysiloxane in the emulsion was a non-flowing soft gel. This emulsion (silicone composition) had a structure represented by the above formula (A) with a molecular weight of about 250,000 from the viscosity of the toluene solution.

[0069] [Comparative Production Example 2] An emulsion of a copolymer with a nonvolatile content of 40% was obtained by adding 840 g of vinyl chloride, 16.8 g of 2-hydroxyethyl methacrylate, and potassium peroxodisulfate to a polymerization vessel equipped with a stirrer, condenser, thermometer and nitrogen gas inlet, and reacting at 45 °C for 30 hours.

[0070] [Comparative Production Example 3] 1200 g of octamethylcyclotetrasiloxane, 0.96 g of γ-methacryloxypropylmethyldimethoxysilane, a solution prepared by dissolving 12 g of sodium lauryl sulfate in 108 g of pure water, and a solution prepared by dissolving 12 g of dodecylbenzenesulfonic acid in 108 g of pure water were charged into a 2 L polyethylene beaker and uniformly emulsified with a homomixer. Then, 400 g of water was gradually added and diluted, and the mixture was passed through a high-pressure homogenizer twice at a pressure of 300 kgf / cm 2 to obtain a uniform white emulsion. This emulsion was transferred to a 2 L glass flask equipped with a stirrer, a thermometer, and a reflux condenser, and a polymerization reaction was carried out at 55 °C for 24 hours. After aging at 15 °C for 24 hours, it was neutralized to pH 7 with a 10% aqueous sodium carbonate solution. The non-volatile content of this emulsion after drying at 105 °C for 3 hours was 45%, and the organopolysiloxane in the emulsion was a non-flowing soft gel. This emulsion (silicone composition) had a structure represented by formula (B) with a molecular weight of about 250,000 from the viscosity of the toluene solution. Furthermore, 226.8 g of methyl methacrylate and 4.6 g of 2-hydroxyethyl methacrylate were added dropwise to this emulsion over 3 to 5 hours, and the reaction was carried out at 27 °C using t-butyl hydroperoxide to graft copolymerize acrylic onto the above silicone composition, obtaining an emulsion of an acrylic-silicone graft copolymer with a non-volatile content of 30%.

[0071] [Comparative Production Example 4] 160 g of the silicone emulsion obtained in the above Comparative Production Example 1 and 75 g of the vinyl chloride emulsion obtained in the above Comparative Production Example 2 were stirred and mixed for 1 hour to obtain a mixed emulsion with a non-volatile content of 42.7%.

[0072] The emulsions obtained in the above Production Examples 1 to 6 and Comparative Production Examples 1 to 4 were evaluated by the following method. The results are shown in Tables 1 and 2.

[0073] [Solid Content Measurement Method] Accurately weigh approximately 1 g of the sample into a dish made of aluminum foil, place it in a dryer maintained at approximately 105°C, heat for 1 hour, take it out of the dryer, allow it to cool in a desiccator, weigh the mass of the aluminum foil dish containing the dried sample, and calculate the solid content (evaporation residue) using the following formula.

Equation

[0074] <Viscosity measurement method> Keep the liquid temperature of the sample at 23 ± 0.5°C and measure it with a rotational viscometer (No. 1 rotor, 6 rpm, manufactured by Toki Sangyo Co., Ltd.: product name: VISCOMETER TVB-10).

[0075] <Average particle size> Weigh 0.01 g of the sample and measure the average particle size (the value of the particle size corresponding to 50% of the particle size cumulative distribution) under the conditions of a circulation flow rate of 2 and a stirring speed of 2 using a laser diffraction particle size distribution analyzer (manufactured by Horiba, Ltd., product name: LA-950V2). [Measurement conditions] Measurement temperature: 25 ± 1°C Solvent: Ion-exchanged water

[0076] <Measurement of the minimum film-forming temperature (MFT)> The minimum film-forming temperature (MFT, °C) of the emulsion was measured by a method conforming to JIS K-6828-2. Specifically, a simple film-forming temperature measuring device (manufactured by Imoto Seisakusho) in which a heating source and a cooling source were installed at a certain distance was used. 1 μl of the emulsion was applied to an aluminum foil, and the state of the coating film after 2 hours was observed using the device. The emulsion was dried under temperature control to form a film, and the boundary temperature between the transparent part where the film was formed and the part where the film was not formed was measured and taken as the minimum film-forming temperature (MFT, °C). Considering the drying property during film formation, an MFT of 100 °C or lower is desirable.

[0077] [Table 1]

[0078] [Table 2]

[0079] [Example 1] (I) As a urethane resin emulsion, Hydran WLS-213 (a polycarbonate-based aqueous urethane resin manufactured by DIC Corporation) was used. While this resin emulsion was being stirred, the vinyl chloride-silicone copolymer resin emulsion obtained in Production Example 1 was added. After stirring for 10 minutes or more, it was filtered through an 80-mesh sieve to obtain the coating composition for Example 1.

[0080] [Examples 2 to 9, Comparative Examples 1 to 7] The coating compositions for each example were produced in the same manner as in Example 1 according to the blending ratios of the respective components shown in Table 3 (Examples 1 to 6), Table 4 (Examples 7 to 9), Table 5 (Comparative Examples 1 to 5), and Table 6 (Comparative Examples 6 to 7). Note that the raw material ratios shown in Tables 3, 4, and 5 are mass ratios based on the solid content.

[0081] [Example 10] (I) As an acrylic-vinyl chloride emulsion, Vinibran 700 (manufactured by Nisshin Chemical Co., Ltd.) was used. While stirring this resin emulsion, the vinyl chloride-silicone copolymer resin emulsion obtained in Production Example 3 was added. After stirring for 10 minutes or more, it was filtered through an 80-mesh sieve to obtain the coating composition of Example 10 (Table 4).

[0082] [Example 11, Comparative Example 8] According to the compounding ratios of the respective components shown in Table 4 (Example 11) and Table 5 (Comparative Example 8), the coating compositions of each example were produced in the same manner as in Example 10.

[0083] The "haze value · haze increase rate" and "static and dynamic friction coefficients" of the coating compositions of each obtained example and each comparative example were measured. The numerical values are shown in Tables 3 to 6. Each measurement was carried out as follows.

[0084] [Film-forming method] The coating composition of each example was applied with a bar coater and dried at 105°C for 3 minutes to form a coating film on each base material of a PET film and a soft vinyl chloride sheet so that the dry film thickness would be approximately 10 μm.

[0085] [Alcohol resistance] The coating compositions of each example and comparative example were applied to a PET film with a bar coater and dried at 105°C for 3 minutes to form a coating film so that the film thickness after drying would be approximately 10 μm. 98% ethanol was dropped onto the coating film and air-dried at room temperature overnight. The change in the coating film after air-drying was visually evaluated. ○: No change in appearance △: Traces remain but no whitening ×: Whitening

[0086] [Water contact angle measurement] The coating compositions of each example and comparative example were applied to a PET film with a bar coater and dried at 105°C for 3 minutes to form a coating film so that the film thickness after drying would be approximately 10 μm. 2 μl of pure water was dropped onto the coating film, and the contact angle values after 1 second and 30 seconds were measured using a contact angle meter CA-D type manufactured by Kyowa Interface Science Co., Ltd. Considering the prevention of adhesion of aqueous stains due to water repellency, a contact angle of 80° (degrees) or more is preferable.

[0087] <Measurement of haze value> The coating compositions of each example and comparative example were applied to a PET film (haze value 2.20) using a bar coater, dried at 105 °C for 3 minutes, and a coating film was formed to be about 10 μm thick when dry. The haze value of the substrate having the coating film of the coating composition of each of the above examples was measured using the product name "Haze Meter COH400" (manufactured by Nippon Denshoku Industries Co., Ltd.).

[0088] <Measurement of static and dynamic friction coefficients> The coating compositions of each example and comparative example were applied to a PET film using a bar coater, dried at 105 °C for 3 minutes, and a coating film was formed to be about 10 μm thick after drying. Using HEIDON TYPE-38 (manufactured by Shinto Kagaku Co., Ltd.), a 200 g metal indenter was brought into perpendicular contact with the above coating film, and the frictional force when it was moved at 3 cm / min was measured, and the friction coefficient was calculated from the frictional force. Incidentally, the preferable range of the static and dynamic friction coefficients under the above conditions is that the static friction coefficient is 0.2 or less and the dynamic friction coefficient is 0.1 or less.

[0089] <Wear resistance> The condition of the coating film was confirmed (visually) for color transfer by rubbing a cotton canvas on the coating film formed on a soft vinyl chloride synthetic leather sheet. The friction conditions were carried out at 9.8 N for 2000 times. ◎: Excellent 〇: Good △: Fair ×: Poor

[0090]

Table 3

[0091]

Table 4

[0092]

Table 5

[0093]

Table 6

Claims

Claim 1 A coating composition containing the following component (I) and component (II). (I) At least one emulsion selected from a vinyl chloride resin emulsion, an acrylic resin emulsion, and a urethane resin emulsion: 60 to 99% by mass of solid content (II) A graft copolymer of (A) an organopolysiloxane represented by the following formula (1) and (B) vinyl chloride, wherein the mass ratio of the (A) organopolysiloxane to the (B) vinyl chloride is (A):(B)=5:95 to 95:5, a vinyl chloride-silicone graft copolymer resin emulsion: 1 to 40% by mass of solid content 【Chemical 1】 (In formula (1), R 1 are the same or different substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, R 2 is a radical reactive functional group. X is the same or different, substituted or unsubstituted, monovalent hydrocarbon group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, or hydroxyl group. Y is X or -[O-Si(X) 2 ] d -X, which may be the same or different. Z is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. a is a number from 0 to 10,000, b is a number from 100 to 10,000, c is a number from 0.0001 to 100, and d is a number from 1 to 1,000. Claim 2 A cured product of the coating composition according to Claim 1. Claim 3 The cured product according to Claim 2, wherein the cured product is a coating film. Claim 4 A laminate having the cured product according to Claim 2. Claim 5 A laminate having the cured product according to Claim 3.

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